JP2748497B2 - Method for producing oxytitanium phthalocyanine crystal - Google Patents
Method for producing oxytitanium phthalocyanine crystalInfo
- Publication number
- JP2748497B2 JP2748497B2 JP3808789A JP3808789A JP2748497B2 JP 2748497 B2 JP2748497 B2 JP 2748497B2 JP 3808789 A JP3808789 A JP 3808789A JP 3808789 A JP3808789 A JP 3808789A JP 2748497 B2 JP2748497 B2 JP 2748497B2
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- JP
- Japan
- Prior art keywords
- oxytitanium phthalocyanine
- crystal
- phthalocyanine crystal
- acid
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Photoreceptors In Electrophotography (AREA)
Description
【発明の詳細な説明】 <産業上の利用分野> 本発明はオキシチタニウムフタロシアニン結晶の製造
法に関し、特に電子写真用感光体に通したオキシチタニ
ウムフタロシアニン結晶の新規な製造法に関する。The present invention relates to a method for producing an oxytitanium phthalocyanine crystal, and more particularly to a novel method for producing an oxytitanium phthalocyanine crystal through an electrophotographic photoreceptor.
<従来の技術> オキシチタニウムフタロシアニンの結晶型には、製造
条件によって準安定なα型と安定なβ型が存在すること
はつとに知られるところである。そしてこれらのオキシ
チタニウムフタロシアニンの結晶型が機械的ひずみ、有
機溶剤および熱の影響下に、相互に結晶型が転移するこ
とも知られている。例えばα型のオキシチタニウムフタ
ロシアニンはN−メチルピロリドン等の有機溶剤中で加
熱することによりβ型に転移する。<Prior Art> It is known that oxytitanium phthalocyanine has a metastable α-form and a stable β-form depending on production conditions. It is also known that the crystal forms of these oxytitanium phthalocyanines mutually shift under the influence of mechanical strain, organic solvents and heat. For example, α-type oxytitanium phthalocyanine transfers to β-type by heating in an organic solvent such as N-methylpyrrolidone.
また、α型のオキシチタニウムフタロシアニンを水性
懸濁液となし、これに芳香族炭化水素溶剤を添加し加熱
処理することによって、X線回折スペクトルにおいてブ
ラッグ角(2θ)27.3゜に強いピークを示すα型にもβ
型にも分類されない結晶型のオキシチタニウムフタロシ
アニンが得られ、かかる結晶型のオキシチタニウムフタ
ロシアニンが光ディスク用記録材料への応用が期待され
る等有用なものであることが特開昭63−20365号公報に
記載されている。Further, an α-type oxytitanium phthalocyanine is converted into an aqueous suspension, an aromatic hydrocarbon solvent is added to the aqueous suspension, and the mixture is subjected to a heat treatment, whereby an α-ray showing a strong peak at a Bragg angle (2θ) of 27.3 ° in an X-ray diffraction spectrum. Type also β
JP-A-63-20365 discloses that a crystalline oxytitanium phthalocyanine which is not classified into a type can be obtained, and that such a crystalline oxytitanium phthalocyanine is useful, such as being expected to be applied to a recording material for an optical disk. It is described in.
<発明が解決しようとする課題> 本発明は従来知られていなかった新規な方法で、電子
写真用感光体等の用途に有用なオキシチタニウムフタロ
シアニン結晶型を製造する工業的有利な製造法を提供す
ることを目的とするものである。<Problems to be Solved by the Invention> The present invention provides an industrially advantageous method for producing an oxytitanium phthalocyanine crystal form useful for applications such as electrophotographic photoreceptors by a novel method which has not been known in the past. It is intended to do so.
<課題を解決するための手段> 本発明の要旨は、オキシチタニウムフタロシアニンを
脂肪族カルボン酸溶媒中、硫酸またはR・SO3H(式中、
Rは置換基を有していてもよい脂肪族または芳香族の残
基を表す。)で表されるスルホン化物とともに加熱処理
してX線回折スペクトルにおいてブラッグ(2θ±0.2
゜)27.3゜に主たる回折ピークを示す結晶を取得するこ
とを特徴とするオキシチタニウムフタロシアニン結晶の
製造法に存する。<Means for Solving the Problems> The gist of the present invention is to provide oxytitanium phthalocyanine in an aliphatic carboxylic acid solvent, sulfuric acid or R.SO 3 H (wherein,
R represents an aliphatic or aromatic residue which may have a substituent. ), And heat-treated with a sulfonate represented by the formula (1) to obtain a Bragg (2θ ± 0.2)
Ii) A method for producing an oxytitanium phthalocyanine crystal characterized by obtaining a crystal having a main diffraction peak at 27.3 °.
<作 用> 以下本発明をさらに詳細に説明する。<Operation> Hereinafter, the present invention will be described in more detail.
本発明方法の原料とするオキシチタニウムフタロシア
ニンはα型、β型または他のいずれの結晶型でもよく、
非晶質のものを用いてもよい。Oxytitanium phthalocyanine as a raw material of the method of the present invention may be α-type, β-type or any other crystal type,
An amorphous material may be used.
用いられる脂肪族カルボン酸としては、酢酸、プロピ
オン酸、酪酸、吉草酸等が挙げられる。好ましくは酢酸
であり、用いる量は原料とするオキシチタニウムフタロ
シアニンに対し10倍〜100倍(重量比)であり、好まし
くは20倍〜50倍である。As the aliphatic carboxylic acid used, acetic acid, propionic acid, butyric acid, valeric acid and the like can be mentioned. Preferably, acetic acid is used, and the amount used is 10 to 100 times (weight ratio), preferably 20 to 50 times, the amount of oxytitanium phthalocyanine used as a raw material.
また、R・SO3Hで表わされるスルホン化物としては、
例えばメタンスルホン酸、エタンスルホン酸、プロパン
スルホン酸、ブタンスルホン酸等の脂肪族スルホン酸類
および下記式で表わされる芳香族スルホン酸類等が挙げ
られる。Further, as a sulfonated product represented by R.SO 3 H,
Examples thereof include aliphatic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and butanesulfonic acid, and aromatic sulfonic acids represented by the following formula.
(式中、R1,R2は水素原子;水酸基;ニトロ基;メチル
基、エチル基、プロピル基等のアルキル基;メトキシ
基、エトキシ基等のアルコキシ基;フッ素原子、塩素原
子、臭素原子等のハロゲン原子;カルボキシル基;シア
ノ基;アミノ基;ジメチルアミノ基等が挙げられる。)
中でもトルエンスルホン酸が好適である。用いる量はオ
キシチタニウムフタロシアニンに対し1.5倍モル〜15倍
モルであり、好ましくは3倍モル〜5倍モルである。 (Wherein R 1 and R 2 are a hydrogen atom; a hydroxyl group; a nitro group; an alkyl group such as a methyl group, an ethyl group, and a propyl group; an alkoxy group such as a methoxy group and an ethoxy group; a fluorine atom, a chlorine atom, and a bromine atom. A carboxyl group; a cyano group; an amino group; a dimethylamino group, and the like.)
Among them, toluenesulfonic acid is preferred. The amount used is 1.5 to 15 moles, preferably 3 to 5 moles relative to oxytitanium phthalocyanine.
本発明方法においては、脂肪族カルボン酸溶媒中での
加熱処理は、溶媒の沸点に近い温度で充分行うほど目的
の結晶型のオキシチタニウムフタロシアニンが確実に得
られるが、工業的には、50〜200℃、好ましくは70〜130
℃で1時間〜5時間加熱処理すれば充分である。In the method of the present invention, the heat treatment in the aliphatic carboxylic acid solvent is carried out sufficiently at a temperature close to the boiling point of the solvent, so that the desired crystal form of oxytitanium phthalocyanine can be obtained with certainty. 200 ° C, preferably 70-130
It is sufficient to perform the heat treatment at a temperature of 1 hour to 5 hours.
尚、本発明において「主たる回折ピーク」とは、その
X線回折スペクトルにおける強度が一番強い(高い)ピ
ークを指す。又、本発明方法によって得られたオキシチ
タニウムフタロシアニン結晶の粉末X線スペクトルの例
を第1図、第4図に示す。電子写真感光体に用いるに
は、ブラッグ角(2θ±0.2゜)27.3゜の回折ピークが
主たるピークであり、そのピーク以外は細かい条件によ
って種々ふれるが、第1図及び第4図の様に27.3゜のピ
ーク強度に対していずれのピークもその強度(ピーク高
さの比較)が50%以下であるスペクトルを示すオキシチ
タニウムフタロシアニン結晶が帯電性、感度等の点から
好ましい。In the present invention, the “main diffraction peak” refers to a peak having the highest (highest) intensity in the X-ray diffraction spectrum. FIGS. 1 and 4 show examples of powder X-ray spectra of the oxytitanium phthalocyanine crystal obtained by the method of the present invention. For use in an electrophotographic photoreceptor, the main peak is a diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.3 °. Other than the peak, various fluctuations occur depending on fine conditions, but as shown in FIG. 1 and FIG. An oxytitanium phthalocyanine crystal showing a spectrum in which the intensity (comparison of peak heights) of all peaks is 50% or less with respect to the peak intensity of ゜ is preferable from the viewpoint of chargeability, sensitivity and the like.
<実施例> 次に本発明を実施例と応用例により更に具体的に説明
するが、本発明はその要旨をこえない限り以下の実施例
に限定されるものではない。<Examples> Next, the present invention will be described more specifically with reference to examples and application examples, but the present invention is not limited to the following examples unless the gist is exceeded.
実施例1 β型オキシチタニウムフタロシアニン5.0gに、p−ト
ルエンスルホン酸25gおよび酢酸500mlを加え、5時間加
熱還流させた。過後、物を水500mlで熱水懸洗し、
続いてメタノール500ml中で熱懸洗した。得られたオキ
シチタニウムフタロシアニン(収量4.2g)のX線回折ス
ペクトル(第1図)は、α型およびβ型オキシチタニウ
ムフタロシアニンのスペクトル(第2,3図)とは異な
り、ブラッグ角(2θ±0.2゜)27.3゜に主たる回折ピ
ークを示すものであった。Example 1 25 g of p-toluenesulfonic acid and 500 ml of acetic acid were added to 5.0 g of β-oxytitanium phthalocyanine, and the mixture was heated under reflux for 5 hours. After a long time, wash things with 500 ml of hot water,
Subsequently, the mixture was hot-washed in 500 ml of methanol. The X-ray diffraction spectrum (FIG. 1) of the obtained oxytitanium phthalocyanine (yield 4.2 g) was different from the spectra of α-type and β-type oxytitanium phthalocyanine (FIGS. 2 and 3), and the Bragg angle (2θ ± 0.2 Ii) The main diffraction peak was shown at 27.3 °.
実施例2 β型オキシチタニウムフタロシアニン5.0gに、メタン
スルホン酸5.0gおよび酢酸100mlを加え、5時間加熱還
流させた。過後物を水200mlで熱水懸洗し、続いて
メタノール200ml中で熱懸洗した。得られたオキシチタ
ニウムフタロシアニン(収量3.9g)のX線回折スペクト
ルを第4図に示す。Example 2 5.0 g of methanesulfonic acid and 100 ml of acetic acid were added to 5.0 g of β-oxytitanium phthalocyanine, and the mixture was refluxed for 5 hours. The residue was hot-washed with 200 ml of water and subsequently hot-washed with 200 ml of methanol. FIG. 4 shows an X-ray diffraction spectrum of the obtained oxytitanium phthalocyanine (yield: 3.9 g).
実施例3 溶媒およびスルホン化物として表に記載したものを用
いる以外実施例1および実施例2と全く同様にしたとこ
ろ、いずれもX線回折スペクトルにおいてブラッグ角
(2θ±0.2゜)27.3゜に主たるピークを示すオキシチ
タニウムフタロシアニンが得られた。Example 3 The same procedure as in Examples 1 and 2 was carried out except that the solvents and sulfonated compounds described in the table were used. In each case, the main peak was at a Bragg angle (2θ ± 0.2 °) of 27.3 ° in the X-ray diffraction spectrum. The following oxytitanium phthalocyanine was obtained.
応用例1 実施例1で製造したオキシチタニウムフタロシアニン
結晶0.4g、ポリビニルブチラール0.2gを4−メトキシ−
4−メチル−2−ペンタノン30gと共に、サンドグライ
ンダーで分散し、この分散液をポリエステルフィルム上
に蒸着したアルミ蒸着層の上にフィルムアプリケータに
より乾燥膜厚が0.3g/m2となる様に塗布、乾燥し、電荷
発生層を形成した。 Application Example 1 0.4 g of the oxytitanium phthalocyanine crystal and 0.2 g of polyvinyl butyral produced in Example 1
Disperse it in a sand grinder together with 30 g of 4-methyl-2-pentanone, and apply this dispersion on an aluminum deposition layer deposited on a polyester film using a film applicator so that the dry film thickness becomes 0.3 g / m 2. After drying, a charge generation layer was formed.
この電荷発生層の上に、N−メチル−3−カルバゾー
ルカルバルデヒドジフェニルヒドラゾン90部、ポリカー
ボネート樹脂(三菱ガス化学社製、商品名ユーピロンE
−2000)100部からなる膜厚17μmの電荷移動層を積層
し、積層型の感光層を有する電子写真感光体を得た。On this charge generation layer, 90 parts of N-methyl-3-carbazolecarbaldehyde diphenylhydrazone, a polycarbonate resin (manufactured by Mitsubishi Gas Chemical Company, trade name Iupilon E)
-2000) 100 parts of a 17 μm-thick charge transfer layer were laminated to obtain an electrophotographic photosensitive member having a laminated photosensitive layer.
この感光体の感度として半減露光量(E1/2)を静電複
写紙試験装置(川口電機製作所製モデルSP−428)によ
り測定した。すなわち、暗所でコロナ電流が50μAにな
る様に設定した印加電圧によるコロナ放電により感光体
を負帯電し、次いで0.125μW/cm2の強度を持つ775nmの
単色光により露光し表面電位が−500Vから−250Vに半減
するのに要した露光量(E1/2)を求めたところ0.22μJ/
cm2であった。The half-life exposure (E1 / 2) was measured as the sensitivity of this photoreceptor using an electrostatic copying paper tester (Model SP-428, manufactured by Kawaguchi Electric Works). That is, the photoreceptor is negatively charged by corona discharge with an applied voltage set so that the corona current becomes 50 μA in a dark place, and is then exposed to 775 nm monochromatic light having an intensity of 0.125 μW / cm 2 and the surface potential is −500 V The exposure dose (E1 / 2) required to halve the voltage to -250 V was calculated to be 0.22 μJ /
It was cm 2.
この時の感光体の帯電圧(初期表面電位)は672Vであ
り露光10秒後の表面電位(残留電位)は−7Vであった。At this time, the charged voltage (initial surface potential) of the photoconductor was 672 V, and the surface potential (residual potential) after exposure for 10 seconds was -7 V.
応用例2 用いるオキシチタニウムフタロシアニン結晶を実施例
2で製造された結晶とおきかえた以外は前記応用例1と
全く同様にしたところ測定された半減露光量(E1/2)は
0.25μJ/cm2であった。Application Example 2 Except that the oxytitanium phthalocyanine crystal used was replaced with the crystal produced in Example 2, the half-exposure dose (E1 / 2) measured was exactly the same as in Application Example 1 described above.
It was 0.25 μJ / cm 2 .
<発明の効果> 本発明方法によれば、ブラッグ角(2θ±0.2度)27.
3度に主たる回折ピークを有するオキシフタロシアニン
結晶を一段階の処理で収率よく得ることができる等工業
的有利に製造可能である。<Effect of the Invention> According to the method of the present invention, the Bragg angle (2θ ± 0.2 degrees) 27.
Oxyphthalocyanine crystals having three major diffraction peaks can be obtained in an industrially advantageous manner, for example, by obtaining a single-stage treatment with good yield.
又、この様にして得られるオキシチタニウムフタロシ
アニン結晶を電荷発生材料として用いる電子写真用感光
体は高感度で、残留電位が低く帯電性が高く、かつ、繰
返しによる変動が小さく、特に、画像濃度に影響する帯
電安定性が良好であることから、高耐久性感光体として
用いることができる。又750〜800nmの領域の感度が高い
ことから、特に半導体レーザプリンタ用感光体に適して
いる。Further, the electrophotographic photoreceptor using the oxytitanium phthalocyanine crystal thus obtained as a charge generation material has high sensitivity, low residual potential, high chargeability, and small variation due to repetition. Since the influence of the charging stability is good, it can be used as a highly durable photoconductor. Also, since the sensitivity is high in the range of 750 to 800 nm, it is particularly suitable for a photoreceptor for a semiconductor laser printer.
第1図および第4図は、実施例1および実施例2で得ら
れた本発明の結晶型オキシチタニウムフタロシアニンの
X線回折スペクトルを示す。第2図および第3図はそれ
ぞれ公知のα型およびβ型オキシチタニウムフタロシア
ニンのX線回折スペクトルを示す。1 and 4 show X-ray diffraction spectra of the crystalline oxytitanium phthalocyanine of the present invention obtained in Examples 1 and 2. 2 and 3 show X-ray diffraction spectra of known α-type and β-type oxytitanium phthalocyanines, respectively.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 竹内 昌子 神奈川県横浜市緑区鴨志田町1000番地 三菱化成株式会社総合研究所内 (56)参考文献 特開 平2−215866(JP,A) ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Masako Takeuchi 1000 Kamoshita-cho, Midori-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Research Institute (56) References JP-A-2-215866 (JP, A)
Claims (1)
カルボン酸溶媒中、硫酸またはR・SO3H(式中、Rは置
換基を有していてもよい脂肪族または芳香族の残基を表
す。)で表されるスルホン化物とともに加熱処理してX
線回折スペクトルにおいてブラッグ角(2θ±0.2゜)2
7.3゜に主たる回折ピークを示す結晶を取得することを
特徴とするオキシチタニウムフタロシアニン結晶の製造
方法。1. An oxytitanium phthalocyanine in an aliphatic carboxylic acid solvent in sulfuric acid or R.SO 3 H (wherein R represents an aliphatic or aromatic residue which may have a substituent). Heat-treated with a sulfonate represented by the formula X
Angle in X-ray diffraction spectrum (2θ ± 0.2 °) 2
A method for producing an oxytitanium phthalocyanine crystal, which comprises obtaining a crystal having a main diffraction peak at 7.3 °.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3808789A JP2748497B2 (en) | 1989-02-17 | 1989-02-17 | Method for producing oxytitanium phthalocyanine crystal |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3808789A JP2748497B2 (en) | 1989-02-17 | 1989-02-17 | Method for producing oxytitanium phthalocyanine crystal |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02215867A JPH02215867A (en) | 1990-08-28 |
JP2748497B2 true JP2748497B2 (en) | 1998-05-06 |
Family
ID=12515694
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3808789A Expired - Fee Related JP2748497B2 (en) | 1989-02-17 | 1989-02-17 | Method for producing oxytitanium phthalocyanine crystal |
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JP (1) | JP2748497B2 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69006961T2 (en) * | 1989-07-21 | 1994-06-23 | Canon Kk | Oxytitanium phthalocyanine, process for its preparation and use of this electrophotoconductive element. |
US5290928A (en) * | 1990-11-22 | 1994-03-01 | Fuji Xerox Co., Ltd. | Process for preparing oxytitanium phthalocyanine hydrate crystal |
JP6368134B2 (en) * | 2014-04-25 | 2018-08-01 | キヤノン株式会社 | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
CN113092228A (en) * | 2021-03-23 | 2021-07-09 | 宁波创润新材料有限公司 | Titanium crystal sample for GDMS detection and preparation method thereof |
-
1989
- 1989-02-17 JP JP3808789A patent/JP2748497B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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JPH02215867A (en) | 1990-08-28 |
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